CN107537455B - A kind of method for the preparation of magnetic Nano biological adsorption agent and its adsorption of Low Concentration uranium that amidoxim is modified - Google Patents
A kind of method for the preparation of magnetic Nano biological adsorption agent and its adsorption of Low Concentration uranium that amidoxim is modified Download PDFInfo
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- CN107537455B CN107537455B CN201710962737.5A CN201710962737A CN107537455B CN 107537455 B CN107537455 B CN 107537455B CN 201710962737 A CN201710962737 A CN 201710962737A CN 107537455 B CN107537455 B CN 107537455B
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Abstract
The present invention relates to the methods of the preparation of magnetic Nano biological adsorption agent and its adsorption of Low Concentration uranium of a kind of modification of amidoxim.Using amidoxim to magnetic Nano Fe3O4It is modified, then by the nanometer Fe of modified amidoxim3O4It is grafted on aspergillus niger by cross-linking reaction, obtains the magnetic Nano Fe of amidoxim modification3O4Aspergillus niger biological adsorption agent.Lone pair electrons on the electron-donating group of amidoxime group adsorbent can form coordinate bond or stable structure with uranyl ion, so as to effectively improve material to the adsorption rate and adsorption capacity of uranyl ion.Present invention incorporates the close uranium performances and nanometer Fe of aspergillus niger3O4Magnetic properties and amidoxime group to the highly selective and affinity of uranium the advantages of, and aspergillus niger is biomaterial, with good adsorption performance, it is easy to operate, production cost is low, low energy consumption, is easy to the advantages that being separated by solid-liquid separation, which has a good application prospect in radioactive pollution prevention and control and uranium recycling field.
Description
Technical field
The present invention relates to the preparation of functional magnetic nano meter biomaterial and the adsorption treatment fields of uranium polluted-water, specifically relate to
And a kind of magnetic Nano Fe modified using amidoxim3O4Preparation and its processing with the biological adsorption agent of aspergillus niger crosslinking is low dense
Spend the method for uranium-containing waste water.
Background technique
Uranium is also a kind of radiation as very important strategic resources in nuclear industry and Application of Nuclear Technology field
Property heavy metal element.A large amount of uranium-containing waste water is supervened during the development and utilization of uranium, the uranium concentration after tentatively administering
Still up to 5mg L-1Left and right, significantly larger than national emission standard.Uranium is as a kind of radiation for having both chemical toxicity and radiotoxicity
Property nucleic if cannot timely and effectively handle will be diffused into the ecosphere with rainwash and underground percolation, through food chain
Transfer endangers ecological environment and human health.Therefore, the method processing low concentration uranium-bearing wastewater of economical and efficient is developed for dimension
Shield ecological environment security and protection human health are of great significance to.
Currently, the processing method of low concentration uranium-bearing wastewater mainly include chemical precipitation method, evaporation concentration method, ion exchange,
Extraction, phytoremediation, membrane separation process and absorption method etc..Absorption method, which refers to, carries out at absorption target substance using adsorbent material
Reason is returned in waste water treatment, air cleaning, rare metal at present so as to the physico-chemical process to object separation and concentration
The fields such as receipts receive significant attention, and are a kind of low concentration uranium method for treating wastewater for having much potentiality.But absorption method is low dense in processing
Spend uranium waste water during there is high production cost, adsorption efficiency is low, recovery utilization rate is not high the defects of.Therefore, it prepares
Economic, efficient, environmental-friendly uranium absorption agent is of great significance.
Nanometer Fe3O4It is a kind of easy preparation and cheap magnetic Nano material, amidoxime group has high selection to uranium
Property and affinity, aspergillus niger be a kind of environmental-friendly close uranium biomaterial.The invention patent selects nanometer Fe3O4For in magnetism
Core, in magnetic Nano Fe3O4Surface modification amidoxime group will then modify the nanometer Fe of amidoxime group3O4Occur with aspergillus niger
Cross-linking reaction, and then prepare a kind of magnetic Nano Fe of amidoxim modification3O4Aspergillus niger biological adsorption agent.Utilize amidoxim pair
Magnetic Nano Fe3O4It is modified, the electron-donating group (- NH of amidoxime group adsorbent2,-C=NOH and-C=NOH) on orphan it is right
Electronics can form coordinate bond or stable structure with uranyl ion, can effectively improve material to the adsorption rate of uranyl ion
And adsorption capacity.Product of the invention combines the close uranium performance and nanometer Fe of aspergillus niger3O4Magnetic properties and amidoxime group
The advantages of to the highly selective and affinity of uranium, has good adsorption performance, and easy to operate, production cost is low, and low energy consumption, is easy to
The advantages that separation of solid and liquid, has a good application prospect in radioactive pollution prevention and control and uranium recycling field.
Summary of the invention
That the present invention provides a kind of adsorption capacities is big, adsorption rate is fast, production cost is low, mechanical strength is big, selectivity is high,
The method of the preparation and its adsorption of Low Concentration uranium of the novel magnetic biological adsorption agent being easily recycled.The preparation process of this adsorbent
It is first to allow FeCl3·6H2O and ethylene glycol mix, and add anhydrous sodium acetate and trisodium citrate, after mixing, are placed in high temperature
In reaction kettle, 200 DEG C of 10 h of reaction obtain nanometer Fe3O4.Again by nanometer Fe3O4With (2- cyanoethyl) triethoxysilane in first
In benzole soln, lead to 100 DEG C of 48 h of reaction under the conditions of nitrogen protection, with hydroxylamine solution amidoximation is occurred into for above-mentioned product and is obtained
The nanometer Fe of amidoxim modification3O4.Then by the nanometer Fe of modified amidoxim3O4It crosslinks and reacts with aspergillus niger, and then
The magnetic Nano Fe modified to amidoxim3O4Aspergillus niger biological adsorption agent.The adsorbent is recycled to adsorb low concentration uranium.
Concrete scheme is as follows:
It is related to the magnetic Nano Fe of amidoxim modification the present invention provides a kind of3O4The preparation of aspergillus niger biological adsorption agent and
The method of its adsorption of Low Concentration uranium, includes the following steps:
(1) 6.8 g FeCl are weighed3·6H2400 ml ethylene glycol are added in conical flask in O, obtain orange after stirring 15min
18 g anhydrous sodium acetates and 5 g trisodium citrates are added in yellow clarified solution body, continue to stir 1 h, it is anti-that solution is poured into high temperature
Answer in kettle, react 10 h at 200 DEG C, after cooled to room temperature, solid product distilled water and ethanol washing for several times, 50
It is dried in vacuo at DEG C for 24 hours, obtains nanometer Fe3O4；
(2) 1 g nanometer Fe is taken3O4 In conical flask, 50 ml toluene solutions are added, after 20 min of ultrasound, addition 1.34
Ml(2- cyanoethyl) triethoxysilane, it is passed through under the conditions of nitrogen protection after 100 DEG C of 48 h of reaction, for several times with ethanol washing, In
The nanometer Fe for having been modified cyano for 24 hours is dried in vacuo at 50 DEG C3O4；
(3) above-mentioned product is reacted at 65 DEG C 5 h with 50 ml azanols (50%), amidoximation occurs, obtains together with amine
The nanometer Fe of oxime modification3O4；
(4) 2 g aspergillus strain powder are weighed in conical flask, the formalin and 50 of 20 ml, 185 g/L is added
The hydrochloric acid solution of 0.12 mol/L of ml, ultrasonic 10min, for use；The nanometer Fe for taking 0.2 g amidoxim to modify3O4It is placed in 45 ml 1
In the NaOH solution of mol/L, after ultrasonic 10min, pour into the stand-by solution of above-mentioned configuration, mixed solution is under the conditions of 50 DEG C
24 h of heating stirring.Solid product is dried in vacuo 24 h after being washed with distilled water for several times at 50 DEG C, obtains amidoxim modification
Magnetic Nano Fe3O4Aspergillus niger biological adsorption agent-ANFAN；
(5) it adsorbs.The magnetic Nano Fe modified using the amidoxim of preparation3O4Aspergillus niger biological adsorption agent is to low concentration uranium
Uranium in waste water is adsorbed, and a certain proportion of adsorbent is specially added into uranium-containing waste water, and concussion is inhaled at a certain temperature
Then attached certain time uses the concentration of spectrophotometer measurement Uranium in Waste Water, calculates its adsorption rate；
(6) using strippant to the magnetic Nano Fe of the amidoxim modification after adsorption uranium3O4Aspergillus niger biological adsorption agent into
Row desorption；Again using the magnetic Nano Fe of the amidoxim modification after desorption3O4Aspergillus niger biological adsorption agent adsorption of Low Concentration uranium is simultaneously
It is desorbed again；After 5 adsorption-desorption cycles, resolution factor is maintained at 93.25% or more；
In the step (1), after anhydrous sodium acetate and trisodium citrate is added, continues to stir 1 h, be to make anhydrous second
Sour sodium and trisodium citrate all dissolve；
In the step (1), it is to make that pyroreaction kettle, which allows its cooled to room temperature after 200 DEG C of 10 h of reaction,
Obtain nanometer Fe3O4It can uniformly be formed in crystallization process；
In the step (2), triethoxysilane reacts with (2- cyanoethyl), so that nanometer Fe3O4Surface grafting cyano；
In the step (3), hydroxylamine solution is added, amidoximation occurs with cyano, obtains amidoxime group；
In the step (4), the making step of aspergillus niger powder is, by black-koji mould living body potato dextrose agar
Fluid nutrient medium (PDA) is cultivated in shaking table, and the temperature setting of shaking table is 30 DEG C, and revolving speed is set as 150 rpm, expands culture
After 60 h, obtained aspergillus strain is cleaned with ultrapure water, is put into 30 DEG C of baking ovens and is dried, after 24 h, is ground with pulverizer
It is broken, cross 100 the polished standard screens, the aspergillus niger powder under collection screen；
In the step (6), using the magnetic Nano Fe of amidoxim modification3O4It is useless that aspergillus niger biological adsorption agent adsorbs uranium-bearing
When uranium in water, the pH value of uranium-containing waste water is 2-9, and when pH value is 5, adsorption effect is best, sees Figure of description 1.Then, to
The adsorbent of certain mass, ratio 0.1-1.0g/L are added in different volumes waste water, optimal ratio is 0.25 g/L, is seen
Figure of description 4.Then, 0-600min is shaken, best to shake the time for 120min, concussion temperature is 25 DEG C, sees that specification is attached
Fig. 5-Fig. 6.Finally, adsorbent and solution is separated using externally-applied magnetic field, complete the absorption to uranium in uranium-containing waste water.
Using the magnetic Nano Fe for the amidoxim modification that the invention patent provides3O4Aspergillus niger biological adsorption agent (ANFAN)
Preparation and its adsorption of Low Concentration uranium method, with use magnetic Nano Fe3O4Aspergillus niger biological adsorption agent (NFAN) absorption is low
Concentration uranium is compared, and the invention patent technology has the advantage that
(1) method that the invention patent provides, higher to the adsorption rate of low concentration uranium under the conditions of Optimal pH, pH value exists
When 2-5 range, as pH value increases, uranium absorption rate increases, and when range of the pH value in 5-9, as pH value increases, adsorption rate has
It is reduced, sees Figure of description 1；
(2) method that the invention patent provides, it is interior at the same time, it is higher to the adsorption rate of low concentration uranium, and in 0-
In 120min, with the extension of time, adsorption rate dramatically increases, in 120-600min, with the extension of time, adsorption rate becomes
Change basicly stable, sees Figure of description 2.The adsorbent that the invention patent provides is than magnetic Nano Fe3O4Aspergillus niger biological adsorption
The adsorption rate of agent is bigger；
(3) method that the invention patent provides, under the conditions of identical temperature, to the adsorption rate of the low concentration uranium in waste water
It is higher, and in the range of 15-55 DEG C, adsorption rate is increased as temperature increases, and sees Figure of description 3.The invention patent mentions
The adsorbent of confession is than magnetic Nano Fe3O4Aspergillus niger biological adsorption agent adsorption rate is higher, adsorption effect is more stable；
(4) method that the invention patent provides, it is higher to the adsorption rate of low concentration uranium under identical initial uranium concentration,
And in the range of 2-6mg/L, with the increase of initial uranium concentration, adsorption rate also increases, and in 6mg/L, adsorption rate reaches most
Greatly, see Figure of description 4.The functionalization adsorbent that the invention patent provides is than magnetic Nano Fe3O4Aspergillus niger biological adsorption agent
Uranium absorption rate is higher, adsorption effect is more preferable；
(5) method that the invention patent provides is right under conditions of optimum absorbent and uranium solution volume (i.e. solid-to-liquid ratio)
The adsorption rate of low concentration uranium in waste water is higher.When solid-to-liquid ratio is in the range of 0.1-1.0 g/L, with the change of solid-to-liquid ratio
Change, adsorption rate also changes therewith, reaches maximum adsorption rate when solid-to-liquid ratio is 0.25g/L, sees Figure of description 5-6.This
The adsorbent that patent of invention provides is than magnetic Nano Fe3O4The adsorption rate of aspergillus niger biological adsorption agent is higher, adsorption effect is more preferable；
(6) method that the invention patent provides is carried out using modification aspergillus niger biological adsorption agent of the strippant to adsorption uranium
Desorption, after parsing, then adsorbs low concentration uranium, after 5 adsorption-desorption cycles, to the resolution factor of low concentration uranium
It is maintained at 93.25% or more, sees Figure of description 7.The reusable property of adsorbent that the invention patent provides is good, service efficiency
It is high.
Detailed description of the invention
Fig. 1 magnetic Nano Fe3O4The magnetism for the amidoxim modification that aspergillus niger biological adsorption agent and the invention patent provide is received
Rice Fe3O4The Contrast on effect of aspergillus niger biological adsorption agent adsorption of Low Concentration uranium under condition of different pH.
Fig. 2 magnetic Nano Fe3O4The magnetism for the amidoxim modification that aspergillus niger biological adsorption agent and the invention patent provide is received
Rice Fe3O4The Contrast on effect of aspergillus niger biological adsorption agent adsorption of Low Concentration uranium in different adsorption times.
Fig. 3 magnetic Nano Fe3O4The magnetism for the amidoxim modification that aspergillus niger biological adsorption agent and the invention patent provide is received
Rice Fe3O4The Contrast on effect of aspergillus niger biological adsorption agent adsorption of Low Concentration uranium at different temperatures.
Fig. 4 magnetic Nano Fe3O4The magnetism for the amidoxim modification that aspergillus niger biological adsorption agent and the invention patent provide is received
Rice Fe3O4Aspergillus niger biological adsorption agent inhales the Contrast on effect of low concentration uranium under different initial uranium concentrations.
Fig. 5-Fig. 6 magnetic Nano Fe3O4The magnetic for the amidoxim modification that aspergillus niger biological adsorption agent and the invention patent provide
Property nanometer Fe3O4The Contrast on effect of aspergillus niger biological adsorption agent low concentration uranium in adsorbed water body under conditions of different dosages.
The magnetic Nano Fe for the amidoxim modification that Fig. 7 the invention patent provides3O4Aspergillus niger biological adsorption agent is in multiple suctions
Corresponding desorption efficiency in attached-desorption cycle.
Specific embodiment
I material
Ferric chloride hexahydrate, ethylene glycol, natrium carbonicum calcinatum, trisodium citrate, (2- cyanoethyl) triethoxysilane, first
Benzene, azanol, formaldehyde, hydrochloric acid, sodium hydroxide, aspergillus niger, benchmark triuranium octoxide
II principle
The principle of the invention are as follows: Fe3O4- the OH on surface is reacted with (2- cyanoethyl) triethoxysilane, obtains surface modification cyanogen
The nanometer Fe of base3O4, then the azanol reaction with addition, so that Fe3O4The cyano on surface generates amidoxime group (- CNOH (NH2)), it obtains
The magnetic Nano Fe modified to amidoxim3O4, then in the presence of formaldehyde crosslinking agent, it is crosslinked with aspergillus niger, to make aspergillus niger
Successfully connect the magnetic Nano Fe of amidoxim modification3O4。
III specific embodiment
The preparation of adsorbent provided by the invention and comprising the concrete steps that for adsorption of Low Concentration uranium:
(1) 6.8 g FeCl are weighed3·6H2400 ml ethylene glycol solutions are added in conical flask in O, after stirring 15min,
Orange-yellow supernatant liquid is obtained, 18 g anhydrous sodium acetates and 5 g trisodium citrates are added, continues to stir 1 h, solution is poured into
In pyroreaction kettle, 10 h are reacted at 200 DEG C, after cooled to room temperature, for several times with distilled water and ethanol washing, at 50 DEG C
Lower vacuum drying for 24 hours, obtains nanometer Fe3O4;
(2) 1 g nanometer Fe is taken3O4 In conical flask, 50 ml toluene solutions are added, after 20 min of ultrasound, addition 1.34
Ml(2- cyanoethyl) triethoxysilane, after being passed through 48 h of the lower 100 DEG C of reactions of condition of nitrogen gas, for several times with ethanol washing, at 50 DEG C
Lower vacuum drying for 24 hours, has been modified the nanometer Fe of cyano3O4;
(3) above-mentioned product is reacted into 5h at 65 DEG C with 50 ml hydroxylamine solutions (50%), amidoximation occurs, obtains together with amine
The nanometer Fe of oxime modification3O4;
(4) 2 g aspergillus strain powder are weighed in conical flask, the formalin and 50 of 20 ml, 185 g/L is added
The hydrochloric acid solution of 0.12 mol/L of ml, ultrasonic 10min, for use；The nanometer Fe for taking 0.2 g amidoxim to modify3O4It is dissolved in 45 ml 1
In the NaOH solution of mol/L, after ultrasonic 10min, pour into the stand-by solution of above-mentioned configuration, mixed solution stirs at 50 DEG C
24 h.It obtains solid and is washed with distilled water the magnetic Nano for being dried in vacuo at 50 DEG C obtain amidoxim modification for 24 hours for several times
Fe3O4Aspergillus niger biological adsorption agent-ANFAN；
(5) it adsorbs.The magnetic Nano Fe modified using the amidoxim of preparation3O4Aspergillus niger biological adsorption agent, to low concentration
Uranium in uranium waste water is adsorbed, and a certain proportion of adsorbent is specially added into uranium-containing waste water, is shaken at a certain temperature
Absorption certain time is swung, the concentration of spectrophotometer measurement Uranium in Waste Water is then used, calculates its adsorption rate.
The preparation for the adsorbent that IV embodiment, 1 the invention patent provides:
(1) preparation of aspergillus niger powder
It by cultured fungus solids inclined-plane, is gently scraped with oese, the bacteria suspension that 500 mL OD values of preparation are 0.1, by thousand
/ bis- inoculum concentration is inoculated into PDA liquid medium, and (30 DEG C, 150 rpm) expand culture 60 h in shaking table,
A large amount of mycelia are grown to media surface, mycelia is taken out, is cleaned with ultrapure water, after being put into 30 DEG C of 24 h of baking oven, uses pulverizer
The standard inspection sieve of milled 100 mesh collects 100 mesh aspergillus niger powder below；
(2) nanometer Fe of amidoxim modification3O4Preparation
Weigh 6.8 g FeCl3·6H2400 ml ethylene glycol solutions are added in conical flask in O, obtain after stirring 15min
18 g anhydrous sodium acetates and 5 g trisodium citrates are added in orange-yellow supernatant liquid, continue to stir 1 h, it is anti-that solution is poured into high temperature
It answers in kettle, reacts 10 h at 200 DEG C, after cooled to room temperature, for several times with distilled water and ethanol washing, the vacuum at 50 DEG C
Drying for 24 hours, obtains nanometer Fe3O4.Take 1 g nanometer Fe3O4 In conical flask, 50 ml toluene solutions are added, after 20 min of ultrasound,
1.34 ml(2- cyanoethyls are added) triethoxysilane, it is passed through under the conditions of nitrogen protection after 100 DEG C of 48 h of reaction, is washed with ethyl alcohol
It washs for several times, the nanometer Fe for having been modified cyano for 24 hours is dried in vacuo at 50 DEG C3O4.By above-mentioned product and 50 ml hydroxylamine solutions
(50%) in 65 DEG C of reaction 5h, amidoximation occurs, obtains the nanometer Fe of amidoxim modification3O4；
(3) the magnetic Nano Fe of amidoxim modification3O4The preparation of aspergillus niger biological adsorption agent -- ANFAN
2 g aspergillus strain powder are weighed in conical flask, the formalin and 50 ml of 20 ml, 185 g/L is added
The hydrochloric acid solution of 0.12 mol/L, ultrasonic 10min, for use；The nanometer Fe for taking 0.2 g amidoxim to modify3O4It is dissolved in 45 ml 1
In the NaOH solution of mol/L, after ultrasonic 10min, pour into the stand-by solution of above-mentioned configuration, mixed solution is under the conditions of 50 DEG C
Stir 24 h.It is washed with distilled water the product for several times, obtained and is dried in vacuo the magnetism for obtaining amidoxim modification for 24 hours at 50 DEG C
Nanometer Fe3O4Aspergillus niger biological adsorption agent -- ANFAN is used for adsorption experiment.
Embodiment 2, pipetting 20 mL initial concentrations respectively is the uranium solution of 10mg/L in 50 mL conical flasks, is successively adjusted
Solution ph is 2,3,4,5,6,7,8,9, in triplicate, adds 0.010 g magnetic Nano Fe respectively3O4Aspergillus niger biology is inhaled
Attached dose/0.010 g the invention patent provide adsorbent, at 25 DEG C revolving speed be 150 rpm constant-temperature shaking incubator in vibrate
Absorption, the timing since being added solution in adsorbent, oscillation 300 min of absorption survey the concentration of wherein remaining uranium.When pH is 2-9,
Magnetic Nano Fe3O4The adsorption rate of aspergillus niger biological adsorption agent is successively 19.17%, 21.61%, 33.33%, 50.85%,
61.83%,76.36%,53.18%,22.92%；The adsorption rate of ANFAN is successively 5.04%, 7.5%, 39.04%, 78.89%,
10.5%,7.39%,6.76%.It follows that magnetic Nano Fe3O4Aspergillus niger biological adsorption agent reaches maximum suction when pH is 7
Attached rate 76.36%, the adsorbent that the invention patent provides reach maximum adsorption rate 78.89% when pH is 5.
Embodiment 3, pipetting 20 mL initial concentrations respectively is the uranium solution of 10 mg/L in 50 mL conical flasks, adjusts it
PH=7 (magnetic Nano Fe3O4Aspergillus niger biological adsorption agent)/pH=5(the invention patent provide adsorbent), add respectively
0.010 g magnetic Nano Fe3O4The adsorbent that aspergillus niger biological adsorption agent/0.010 g the invention patent provides, in triplicate.
Absorption, the timing since being added in solution adsorbent, oscillation absorption are vibrated in the constant-temperature shaking incubator that revolving speed is 150 rpm
300 min, adjusting shaking table temperature respectively is 15 DEG C, 25 DEG C, 35 DEG C, 45 DEG C, 55 DEG C, measures the concentration that uranium is remained in solution.Magnetic
Property nanometer Fe3O4The adsorption rate of aspergillus niger biological adsorption agent is followed successively by 70.16%, 74.06%, 81.2%, 83.15%, 84.4%；This
The adsorption rate for the adsorbent that patent of invention provides is followed successively by 82.19%, 84.98%, 86.54%, 88.19%, 89.65%.Magnetic Nano
Fe3O4The optimal adsorption temperature for the adsorbent that aspergillus niger biological adsorption agent and the invention patent provide is respectively 55 DEG C and 55 DEG C.
Embodiment 4, pipetting 20 mL initial concentrations respectively is the uranium solution of 6 mg/L in 50 mL conical flasks, adjusts its pH
=7 (magnetic Nano Fe3O4Aspergillus niger biological adsorption agent)/pH=5(the invention patent provide adsorbent), add 0.010 respectively
G magnetic Nano Fe3O4The adsorbent that aspergillus niger biological adsorption agent/0.010 g the invention patent provides, revolving speed is at 25 DEG C
Absorption is vibrated in the constant-temperature shaking incubator of 150 rpm, in triplicate.Respectively the time be 15,30,45,60,120,180,240,
300, it is sampled when 600min, measures the concentration for remaining uranium in solution.Magnetic Nano Fe3O4The adsorption rate of aspergillus niger biological adsorption agent
It is followed successively by 21.77%, 26.85%, 34.11%, 39.19%, 49.35%, 65.31%, 78.37%, 79.1%, 80.55%；The present invention is special
The adsorption rate for the adsorbent that benefit provides is followed successively by 43.08%, 64.27%, 67.68%, 78.39%, 89.69%, 89.69%, 89.69%,
89.69%,89.69%.It follows that magnetic Nano Fe3O4The adsorption experiment of aspergillus niger biological adsorption agent reaches after 240min
The adsorption experiment of balance, the adsorbent that the invention patent provides reaches balance after 120min.
Embodiment 5, pipetting 20 mL initial concentrations respectively is the uranium solution of 2,4,6,8,10 mg/L in 50 mL conical flasks
In, adjust its pH=7 (magnetic Nano Fe3O4Aspergillus niger biological adsorption agent)/pH=5(the invention patent provide adsorbent), point
0.010 g magnetic Nano Fe is not added3O4The adsorbent that aspergillus niger biological adsorption agent/0.010 g the invention patent provides, a formula
Three parts.Controlled at 25 DEG C of (magnetic Nano Fe3O4Aspergillus niger biological adsorption agent)/25 DEG C (the invention patent provides
Adsorbent) revolving speed be 150 rpm constant-temperature shaking incubator in oscillation absorption 240min (magnetic Nano Fe3O4Aspergillus niger biology is inhaled
Attached dose)/120min (adsorbent that the invention patent provides), it carries out adsorbent and the absorption of uranium is studied, measure residual in solution
Stay the concentration of uranium, magnetic Nano Fe3O4The adsorption rate of aspergillus niger biological adsorption agent is successively 43.00%, 58.07%, 76.82%,
60.65%,59.49%；The adsorption rate for the adsorbent that the invention patent provides is successively 77.77%, 85.59%, 89.66%,
87.29%,86.51%.It follows that magnetic Nano Fe3O4The adsorbent that aspergillus niger biological adsorption agent and the invention patent provide
Absorption takes the lead in reducing after increasing in given concentration range.
Embodiment 6, pipetting certain volume initial concentration respectively is the uranium solution of 6 mg/L in 50 mL conical flasks, is adjusted
Its pH=7 (magnetic Nano Fe3O4Aspergillus niger biological adsorption agent) adsorbent that provides of/pH=5(the invention patent), adjust magnetic
Nanometer Fe3O4The additional amount for the adsorbent that aspergillus niger biological adsorption agent/the invention patent provides and the ratio of uranium solution volume are (i.e. solid
Liquor ratio) it is respectively 0.05,0.1,0.15,0.2,0.25,0.3g/L (magnetic Nano Fe3O4Aspergillus niger biological adsorption agent) 0.1,
0.2, the adsorbent that 0.25,0.5,1.0 g/L(the invention patent provide), in triplicate.(magnetic controlled at 25 DEG C
Nanometer Fe3O4Aspergillus niger biological adsorption agent)/25 DEG C of (the invention patent provide adsorbent) revolving speeds be 150 rpm constant temperature train
Support oscillation absorption 240min (magnetic Nano Fe in shaking table3O4Aspergillus niger biological adsorption agent) (the invention patent mentions/120min
The adsorbent of confession), it carries out adsorbent and the absorption of uranium is studied, measure the concentration for remaining uranium in solution, magnetic Nano Fe3O4Black song
The adsorption rate of mould biological adsorption agent is respectively 29.06%, 51.01%, 55.16%, 56.35%, 57.53%, 59.31%；The present invention is special
The adsorption rate for the adsorbent that benefit provides is respectively 39.28%, 76.50%, 92.35%, 87.53%, 83.39%.It follows that magnetic
Nanometer Fe3O4The best solid-to-liquid ratio of aspergillus niger biological adsorption agent is 0.3g/L, adsorption rate 59.31%, the invention patent offer
Adsorbent best solid-to-liquid ratio be 0.25g/L.Adsorption rate is 92.35%.
By optimization experiment as can be seen that the adsorption rate of modified adsorbent is greatly increased than unmodified, handling
Low concentration uranium field in waste water, the former is advantageously.
It is above only better embodiment of the invention, according to the above-mentioned design, those skilled in the art
Can also to this various modification can be adapted and transformation.For example, transformation prepares the reaction time of adsorbent, reaction temperature, the present invention is utilized
The adsorbent that patent provides adsorbs other heavy metal ion, and using the method processing high concentration uranium-containing waste water etc..However,
Similar this transformation and modification belongs to essence of the invention.
Claims (9)
1. a kind of preparation of the magnetic Nano biological adsorption agent of amidoxim modification, by the nanometer Fe of modified amidoxime group3O4It is logical
It crosses cross-linking reaction to be grafted on aspergillus niger, which is characterized in that detailed process are as follows:
(1) by FeCl3·6H2O and ethylene glycol mix, and add anhydrous sodium acetate and trisodium citrate, after mixing, are placed in
In pyroreaction kettle, 200 DEG C of 10 h of reaction obtain nanometer Fe3O4；
(2) again by nanometer Fe3O4With 2- cyanoethyl triethoxysilane in toluene solution, lead under the conditions of nitrogen protection 100 DEG C it is anti-
48 h are answered, obtained solid product ethanol washing, vacuum drying is to get to the nanometer Fe for having modified cyano3O4；
(3) amidoximation is occurred into for above-mentioned product and hydroxylamine solution and obtains the nanometer Fe of amidoxim modification3O4；
(4) by the nanometer Fe of modified amidoxim3O4It crosslinks and reacts with aspergillus niger, obtain the magnetic Nano of amidoxim modification
Fe3O4Aspergillus niger biological adsorption agent.
2. a kind of preparation of the magnetic Nano biological adsorption agent of amidoxim modification according to claim 1, which is characterized in that
In the step (1), 6.8 g FeCl are weighed3·6H2400 ml ethylene glycol solutions are added in conical flask in O, stir 15 min
After obtain yellowish orange supernatant liquid, 18 g anhydrous sodium acetates and 5 g trisodium citrates are added into conical flask, continue stirring 1
Solution is poured into pyroreaction kettle after h, reacts 10 h at 200 DEG C, after cooled to room temperature, obtained solid product according to
After secondary use distilled water and ethanol washing, 24 h are dried in vacuo at 50 DEG C to get nanometer Fe is arrived3O4。
3. a kind of preparation of the magnetic Nano biological adsorption agent of amidoxim modification according to claim 1, which is characterized in that
In the step (2), 1 g nanometer Fe is weighed3O4 In conical flask, 50 ml toluene solutions are added, are added after 20 min of ultrasound
1.34 ml2- cyanoethyl triethoxysilanes are passed through the solid product after 100 DEG C of 48 h of reaction, obtained under the conditions of nitrogen protection
It is dried in vacuo at 50 DEG C after for several times with ethanol washing for 24 hours to get to the nanometer Fe for having modified cyano3O4。
4. a kind of preparation of the magnetic Nano biological adsorption agent of amidoxim modification according to claim 1, which is characterized in that
In the step (3), step (2) product is reacted 5 hours, after being cooled to room temperature with 50 ml hydroxylamine solutions at 65 DEG C, is obtained
Solid product 24 h are dried in vacuo after for several times at 50 DEG C with distilled water and ethanol washing successively to get to amidoxim modification
Nanometer Fe3O4。
5. a kind of preparation of the magnetic Nano biological adsorption agent of amidoxim modification according to claim 1, which is characterized in that
In the step (4), weigh 2 g aspergillus strain powder in conical flask, be added 20 ml, 185 g/L formalin and
The hydrochloric acid solution of 50 ml, 0.12 mol/L, ultrasound are stand-by after ten minutes；The nanometer Fe for taking 0.2 g amidoxim to modify3O4It is placed in 45
In the NaOH solution of 1 mol/L of ml, ultrasound is added to after ten minutes in the stand-by solution of former configuration, obtained mixed solution
24 h are stirred at 50 DEG C, obtained solid product is dried in vacuo for 24 hours after being washed with distilled water for several times at 50 DEG C, can be obtained
The magnetic Nano Fe of amidoxim modification3O4Aspergillus niger biological adsorption agent-ANFAN.
6. a kind of preparation of the magnetic Nano biological adsorption agent of amidoxim modification according to claim 1, which is characterized in that
In the step (1), after anhydrous sodium acetate and trisodium citrate is added, continues to stir 1 h, make anhydrous sodium acetate and citric acid three
Sodium all dissolves.
7. a kind of preparation of the magnetic Nano biological adsorption agent of amidoxim modification according to claim 1, which is characterized in that
In the step (1), pyroreaction kettle allows its natural cooling after 200 DEG C of 10 h of reaction, makes nanometer Fe3O4In crystallization process
In can uniformly form.
8. utilizing a kind of magnetic Nano Fe for amidoxim modification that claim 1 is prepared3O4Aspergillus niger biological adsorption agent is inhaled
The method of attached low concentration uranium, which is characterized in that specific steps are as follows:
Absorption, using the magnetic Nano Fe of the obtained amidoxim modification of claim 13O4Aspergillus niger biological adsorption agent is to uranium-bearing
Uranium in waste water is adsorbed, specifically:
The adsorbent that solid-to-liquid ratio is 0.1-1.0 g/L is added into uranium-containing waste water, when shaking 0-600 min at a temperature of 55 DEG C
Between, the concentration of spectrophotometer measurement Uranium in Waste Water is then used, its adsorption rate is calculated,
The pH value of the uranium-containing waste water is 2-9.
9. a kind of magnetic Nano for amidoxim modification being prepared according to claim 8 using claim 1
Fe3O4The method of aspergillus niger biological adsorption agent adsorption of Low Concentration uranium, which is characterized in that
When the pH value of the uranium-containing waste water is 5, adsorption effect is best,
The adsorbent solid-to-liquid ratio optimal proportion is 0.25g/L,
The best concussion time is 120 min；Shaking temperature is 55 DEG C.
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| CN108325505A (en) * | 2018-03-12 | 2018-07-27 | 秋晓东 | A kind of restoration of the ecosystem agent containing amidoxim and its selective enrichment technique to uranyl |
| CN109012586A (en) * | 2018-08-15 | 2018-12-18 | 中国科学院青海盐湖研究所 | Uranium absorption agent and preparation method thereof |
| CN109569548B (en) * | 2018-12-07 | 2022-04-12 | 兰州大学 | Magnetic nano functional material for extracting uranium from seawater and preparation method thereof |
| CN109926024B (en) * | 2019-03-27 | 2022-03-01 | 湖南工学院 | Preparation method and application of magnetic organic modified nano adsorption material |
| CN111482161B (en) * | 2020-04-17 | 2021-04-16 | 青岛理工大学 | Magnetic biological manganese oxide adsorption material and preparation and application thereof |
| CN113600145A (en) * | 2021-07-20 | 2021-11-05 | 山东大学 | Preparation method of antibacterial amidoxime group modified magnetic titanium dioxide core-shell structure adsorbing material |
| CN114849675A (en) * | 2022-05-18 | 2022-08-05 | 哈尔滨工业大学 | Preparation method of magnetic NiFe-LDH composite material for adsorbing uranium |
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